Oxime ethers

ABSTRACT

WHEREIN R1 IS A HYDROGEN ATOM OR A LOWER ALKYL RADICAL; R2 IS AN ALIPHATIC, CYCLOALIPHATIC, AROMATIC OR HETEROCYLIC RADICAL; OR WHEREIN R1 AND R2 FORM PART OF A SATURATED OR UNSATURATED CARBOCYCLE OR A 5-,6-OR 7MEMBERED HETEROCYCLE; R3 IS A NITRO, TRIFLUOROMETHYL, FORMLY, LOWER CARBALKOXY, SULFAMYL OR MONO- OR DI-LOWER ALKYL SULFAMYL ADICAL; R4 AND R5 EACH IS A HYDROGEN OR HALOGEN ATOM, AN AMINO, MONO-OR DI-LOWER ALKYL AMINO, LOWER ALKOXY, CYCLOALKOXY, LOWER ARALKYTHIO OR LOWER ALKYL ARBALKOXY, ARYLTHIO, LOWER ARALKYTHIO OR LOWER ALKYL GROUP, OR 5-6-OR 7-MEMBERED HETEROCYCLE.   1-NO2,2-(R1-C(-R2)=N-O-),3-R5,4-R4,5-R3-BENZENE   NEW OXIME ETHERS AND PESTICIDAL AND HERBICIDAL PREPARATIONS CONTAINING THEM ARE DISCLOSED. THE OXIME ETHERS CORRESPOND TO THE FORMULA

3,813,429 OXIME ETHERS Adolf Hubele, Riehen, Switzerland, assignor toCiba- Geigy AG, Basel, Switzerland No Drawing. Application June 16,1970, Ser. No. 46,832,

now Patent No. 3,733,359, which is a continuation-inpart of abandonedapplication Ser. No. 521,413, Jan. 18, 1966. Divided and thisapplication Mar. 8, 1973, Ser. No. 339,246 Claims priority, applicationSwitzerland, Jan. 22, 1965, 915/65; July 9, 1965, 9,630/ 65 Int. Cl.C07c 101/42 US. Cl. 260-471 R 3 Claims ABSTRACT OF THE DISCLOSURE Newoxime ethers and pesticidal and herbicidal preparations containing themare disclosed. The oxime ethers correspond to the formula wherein R is ahydrogen atom or a lower alkyl radical; R is an aliphatic,cycloaliphatic, araliphatic, aromatic or heterocyclic radical; orwherein R and R form part of a saturated or unsaturated carbocycle or a5-, 6- or 7- membered heterocycle; R is a nitro, trifluoromethyl,formyl, lower carbalkoxy, sulfamyl or monoor di-lower alkyl sulfamylradical; R and R each is a hydrogen or halogen atom, an amino, monoordi-lower alkyl amino, lower alkoxy, cycloalkoxy, lower alkylthio, nitro,lower carbalkoxy, arylthio, lower aralkylthio or lower alkyl group, or5-, 6- or 7-membered heterocycle.

CROSS REFERENCE This is a division of application Ser. No. 46,832, filedon June 16, 1970, now US. Pat. No. 3,733,359, which in turn is acontinuation-in-part of application Ser. No. 521,413, filed Jan. 18,1966, now abandoned.

BACKGROUND OF THE INVENTION The present invention provides new oximeethers and pesticidal preparations containing them. The oxime etherscorrespond to the formula I ia R4 I wherein R is a hydrogen atom or alower alkyl radical; R is an aliphatic, cycloaliphatic, araliphatic,aromatic or heterocyclic radical; or wherein R and R form part of asaturated or unsaturated carbocycle or a 5-, 6- or 7- memberedheterocycle; R is a nitro, trifluoromethyl, formyl, lower carbalkoxy,sulfamyl or monoor di-lower alkylsulfamyl radical; R and R each is ahydrogen or halogen atom, an amino, monoor dilower alkylamino, loweralkoxy, cycloalkoxy, lower alkylthio, nitro, lower carbalkoxy, arylthio,lower aralkylthio group or 5-, 6- or 7-membered heterocycle.

mted States Patent 0 R in the above formula stands for a lower alkylradical. Such radicals contain 1 to 4 carbon atoms and may be branchedor unbranched such as the methyl and ethyl groups or the normal oriso-propyl or butyl group or secondary or tertiary butyl group.Preferred groups, however, are besides the hydrogen atom the methyl andethyl radicals.

R stands for an aliphatic, cycloaliphatic, araliphatic, aromatic orheterocyclic radical. The aliphatic radical may be branched orunbranched, saturated or unsaturated. Preferably such radicals containup to 8 carbon atoms and are alkyl or alkenyl radicals which may besubstituted or unsubstituted. Suitable substituents are for instancehalogen atoms, such as fluorine, chlorine or bromine or hydroxy oralkoxy groups. The cycloaliphatic radicals contain 3 to 8 carbon atomsand may be saturated or unsaturated and monoor polycyclic. As a rulethey contain 3 to 12 carbon atoms and are saturated. They preferably aremonoor bicyclic and have 3 to 7 ring members. The araliphatic radicalscontain in the aromatic moiety at least one benzene nucleus and in thealiphatic moiety preferably an unbranched chain containing 1 to 4 carbonatoms. This aliphatic chain may be saturated or unsaturated, substitutedor unsubstituted. Suitable substituents are hydroxy groups and halogenatoms, such as chlorine and especially bromine. Suitable chains contain2 carbon atoms and are saturated; they may also contain one or twobromine atoms or one double bond. Aromatic radicals are to be understoodas being substituted or unsubstituted phenyl radicals or condensed ringsystems. The preferred embodiment are substituted and unsubstitutedphenyl radicals. Suitable substituents on the phenyl moiety are e.g.halogen atoms such as fluorine and especially chlorine, bromine andiodine; lower alkyl and alkoxy groups containing 1 to 4 carbon atoms;hydroxy groups; amino groups which may be substituted by one or twolower alkyl, lower alkoxyalkyl or lower alkanol radicals; nitro groups;lower alkyl carbamoyl radicals; phenoxy groups which may be substitutedby one or more of the substituents enumerated above for the phenylradical especially by nitro groups. The heterocyclic radicals cominginto consideration particularly are 5- or 6-membered and contain atleast one oxygen or sulfur especially however nitrogen atom. Theseheterocycles may be substituted, preferably by lower alkyl radicals,especially the methyl group. Examples of such heterocycles are i.a.pyridine and quinaldine compounds.

R stands for a trifluoromethyl, formyl, nitro, lower carbalkoxy,sulfamyl or monoor di-lower alkylsulfamyl group. The alkyl moieties ofthe carbalkoxy and alkylsulfamyl group contain 1 to 4 carbon atoms andmay be branched or unbranched. Preferred alkyl moieties contain 1 or 2carbon atoms. However, suitable substituents are not limited to theabove enumeration. Thus also halogenalkyl groups quite generally may beused. Moreover, halogen atoms such as chlorine, bromine and iodine;alkyl groups containing 1 to 6 carbon atoms, the carboxyl group; loweralkylor aryl-, especially phenylcarbamyl groups; the sulfonic acidgroups; and lower alkylsulfonyl groups may be used likewise.

R and R each stands for a hydrogen or halogen atom, a lower alkyl,amino, monoor di-lower alkylamino, lower alkoxy, cycloalkoxy, loweralkylthio, lower carbalkoxy, arylthio, lower aralkylthio, nitro orheterocyclic radical.

The halogen atoms may be elected from fluorine, bromine, iodine andespecially chlorine. The lower alkyl moieties enumerated above contain 1to 4 carbon atoms and may be branched or unbranched. The heterocyclicradicals are 5-, 6- or 7-membered, especially 5- or 6-membered, andcontain as hetero-atoms one or more oxygen, sulfur or especiallynitrogen atoms. Such heterocyclic radicals are i.a. the pyridino andmorpholino radical. The cycloalkoxy radicals are 3 to S-membered,especially however 6-membered. Representative of such radicals is thecyclohexoxy radical. Especially suitable oxime ethers are those whichcorrespond to the formulae wherein R and R have the meanings given aboveand R and R each is hydrogen, lower alkyl, such as methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec.butyl, tert.butyl amyl orcycloalkyl, such as cyclopentyl or cyclohexyl.

From among the compounds of formulae (H) and (III) those are preferredwhich correspond to the formula wherein R and R have the above meanings.More particularly R may stand for hydrogen and R for a substitutedphenyl radical. Such compounds correspond to the formulae X NO:

X N O; QCaHQa X a 4 wherein R R and R have the meanings given above andX and X each stands for halogen. More specifically X representschlorine, bromine and iodine, whereas X stands for chlorine.

The oxime ethers of the formulae (I) to (V1) may be derived fromaliphatic, araliphatic, aromatic or heterocyclic aldehydes or ketones,and also from quinones and endocyclic ketones for example fluorenone,indanone, acenaphthenone, anthronc, N-methylpyridonc, N-methyLpiperidone, furfurol or nitrofurfurol.

Preferred use is made of oxime ethers derived from aliphatic aldehydesor ketone-s, from araliphatic aldehydes or ketones, or from aromatic orheterocyclic aldehydes or ketones.

Suitable aliphatic aldehydes are simply constituted aldehydes forexample acetaldehyde, propionaldehyde, butyraldehyde or aldehydes havinga longer chain, for example heptaldehyde, stearaldehyde or unsaturatedaldehydes for example crotonaldehyde. Suitable aliphatic ketones aresimple ketones for example acetone, methylethyl ketone, hexanone-(fi),diisopropylketone, mesityl oxide, and phorone. Suitable araliphatic oraromatic aldehydes and ketones are cinnamic aldehyde, hydrocinnamicaldehyde, halogen adducts or cinnamic aldehyde for exampledibromo-cinnamic aldehyde, diiodo-cinnamic aldehyde, acetophenone,propiophenone, benzaldehyde, nuclear halogenated, alkylated, nitratedand alkoxylated benzaldehydes. Examples at suitable cyclic ketones arecyclopentanone, cyelohexanone, cycloheptanone as well as their cyanoderivatives. Suitable heterocyclic ketones and aldehydes are, forexample, picoline aldehyde, nicotine aldehyde, isonicotine aldehyde andN-alkylpiperidones.

If such aldehydes or ketones contain aromatic radicals, their suitablysubstituted derivatives may likewise be used. These substituents may beof a non-functional kind, for example halogen atoms, nitro or nitrosogroups, or of a functional kind or derived from functional substituents,being, for example hydroxyl, acyloxy, carbamoyloxy, alkoxy, aryloxy,thiol, acylthio, alkylthio, triiluoromethyl, cyano, formyl, amino,alkylamino, dialkylamino, arylamino, diarylamino, carboxy or carbalkoxygroups.

By virtue of their broad biocidal spectrum the new oxime ethers offerthe special advantage that they are suitable for combating a very widevariety of vegetable and animal pests. They are suitable not only foruse as herbicides, which is the preferred utility, but when used in aconcentration that does not produce any phytotoxic effects, they arevery useful in plant protection for comhating harmful micro-organisms,such as phytopathogenic fungi, for example Alternaria solam',Phytophthora infestans and Septoria apzi, and act also against harmfulinsects, acarides, nematodes and their ova and larvae. They may also beused quite generally as micro-bicides, for example against Aspergillusspecies, and as insecticides, for example against midges and flies.

The oxime ethers according to this invention may be used per se or inadmixture with suitable carriers. Such carriers may be solid or liquid.The pesticidal preparations thus formed may therefore contain a solidcarrier, a solvent diluent, dispersant, wetting agent, adhesive,fertilizer and/ or other known pesticides.

For the manufacture of solutions of compounds of the general formula (I)for direct spraying there may be used, for example, petroleum fractionsof a high to medium boiling range, for example diesel oil or kerosene,coal tar oil and oils of a vegetable or animal origin, as well ashydrocarbons for example alkylated naphthalenes, tetrahydronaphthaleneif desired in conjunction or admixture with xylene mixtures,cyclohexanols, ketones, chlorinated hydrocarbons for exampletrichloroethane or tetrachloroethane, trichloroethylene, triortetrachlorobenzene. It is advantageous to use organic solvents boilingabove 100 C.

Aqueous forms of applications are prepared most advantageously fromemulsion concentrates, pastes or wettable spray powders by addition ofwater. Suitable emulsifying or dispersing agents are non-ionic products,for example condensation products of aliphatic alcohols, amines orcarboxylic acids containing a long-chain hydrocarbon residue of about to20 carbon atoms with ethylene oxide, for example the condensationproduct of octadecyl alcohol with 25 to 30 mols of ethylene oxide, or ofsoybean fatty acid with 30 mols of ethylene oxide, or of commercialoleylamine with mols of ethylene oxide, or of dodecylmercaptan with 12mols of ethylene oxide. From among suitable anionic emulsifiers, theremay be mentioned the sodium salt of dodecyl alcohol sulphuric acidester, the sodium salt of dodecylbenzenesulphonic acid, the potassium ortriethanolamine salt of oleic or abietic acid or of mixtures of theseacids, or the sodium salt of a petroleumsulphonic acid. Suitablecationic dispersants are quaternary ammonium compounds, for examplecetyl pyridinium bromide or dihydroxyethyl benzyl dodecyl ammoniumchloride.

For the manufacture of dusting and casting preparations, there may beused as solid vehicles talcum, kaolin, bentonite, calcium carbonate,calcium phosphate, or coal, cork meal, wood meal or other materials ofvegetable origin. It is also very advantageous to manufacturepreparations in granular form. The various forms of application maycontain the usual additives for improving the distribution, theadhesion, the stability towards rain or the penetration; as suchsubstances there may be mentioned fatty acids, resin, glue, casein andalginates.

The preparations of this invention may be used by themselves or inconjunction or admixture with conventional pesticides, especiallyinsecticides, acaricides, nematocides, bactericides or furtherfungicides or herbicides.

Especially potent herbicides are those preparations which contain asactive ingredient a compound of the formula wherein R represents ahydrogen atom or an aliphatic radical and R an aliphatic radical or anunsubstituted or substituted phenyl group, A represents NO CHO, COOH orC00 alkyl, and B stands for hydrogen, NO COOH, COO alkyl or chlorine.The phenyl radical R may carry various substituents, for example halogenatoms, nitro, alkyl, hydroxyl or alkoxy groups and/ or carbamoyloxygroups.

Particularly potent herbicides are the compounds of the formula (Ia)wherein R and R have the following meanings:

Especially useful acaricides are those preparations which contain asactive ingredient a compound of the formula wherein R represents ahydrogen atom and R a phenyl radical which may be substituted by halogenatoms or alkyl or alkoxy groups, or wherein R and R represent alkylradicals or are part of an isocyclic residue.

Especially potent are the compounds of the formula The activeingredients of formula ('I) may be manufactured according to knownmethods, such as e.g.: A salt of ketoxime or aldoxime of the formulaO-NOMB wherein R; and R, have the above meanings and Me stands for ametal atom, preferably an alkali metal atom,

is reacted with a halogeno-benzene of the formula Hal R:

wherein R to R have the above meanings and Hal represents a fluorine,chlorine, bromine or iodine atom.

The reaction may be carried out in a solvent, for example in ethanol,methanol, acetonitrile or dioxan, as a rule at room temperature; in manycases it is accompanied by a spontaneous rise in temperature. The oximeethers obtained in this manner are very easy to isolate by diluting thereaction solution with water. The ethers precipitate and may, ifdesired, be recrystallized. This process may be varied in that followingupon the formation of the oxime ether one or several groups, R R R R aresubsequently converted.

More especially, halogen atoms R and/or R may be exchanged for compoundscontaining active hydrogen atoms, thus for example for ammonia, primaryor secondary aliphatic, araliphatic or aromatic amines, alcohols,phenols, alkanethiols or thiophenols.

The oxime ethers accessible in this manner may take the syn-form or theanti-form. As a rule, they are obtained in the form of a mixture ofisomers, which can be resolved into the two forms by a usual operation,for example crystallization or adsorption For the manufacture of thepreparations of this invention, it sufiices to use the mixture ofisomers as obtained by the reaction.

The present invention further includes new oxime ethers of the generalformula wherein R and R have the above meanings and R represents atrifluoromethyl, formyl, unsubstituted or substituted carboxyl orpossibly alkylated sulphamyl residue, and R represents a hydrogen atomor a nitro group, or wherein R stands for the nitro group and R for apossibly esterified carboxyl group.

The following examples illustrate the invention.

EXAMPLE 1 CHsO- CH==N-0 NO! A solution of sodium ethylate prepared from11.5 parts of sodium and 500 parts by volume of absolute ethanol isadded to 76 parts of anisaldehyde in 400 parts by volume of absoluteethanol. During 10 minutes at 40 C. 101 parts of4-chloro-1,3-dinitrobenzene in 300 parts by volume of absolute ethanolare added drop by drop, the temperature rising to 65 C. The batch iscooled to room temperature, diluted with water, filtered andrecrystallized from dimethyl-formamide+ethanol. The product melts at187-l87.5 C.

EXAMPLE 2 A solution of sodium ethylate prepared from 13.1 parts ofsodium and 300 parts by volume of absolute ethanol is added drop by dropduring 30 minutes, at room temperature, to a solution of 82 parts ofortho-methoxybenzaldehydeoxime and 115 parts of4-chloro-1,3-dinitrobenzene in 1000 parts by volume of acetonitrile.After 4 hours, the batch is diluted with 3000 parts by volume of water,filtered and recrystallized from toluene+acetone. The product melts at184-184.5 C.

EXAMPLE 3 A solution of sodium ethylate prepared from 18.5 parts ofsodium and 500 parts by volume of absolute ethanol is added drop by dropduring 30 minutes at room temperature to a solution of 90 parts ofcyclohexanonc oxime and 162 parts of 4chloro-1,3-di-nitr0benzene in 500parts by volume of acetonitrile. After 4 hours, the batch is dilutedwith water filtered and recrystallized from acetonitrile. The productmelts at 105.5-106" C.

EXAMPLE 4 A solution of sodium ethylate prepared from 12 parts of sodiumand 250 parts by volume of absolute ethanol is added drop by drop atroom temperature to a solution of 50.5 parts of methyl-isopropoylketonoxime and 101.3 parts of 4-chloro-1,3-dinitrobenzene in 400 partsby volume of acetonitrile, while stirring. After 12 hours, the batch isdiluted with water, filtered and recrystallized from acetonitrile. Theproduct melts at 85 to 86 C.

EXAMPLE 5 EXAMPLE 6 om-ornoumvo-Qno:

An oxime salt solution of 43.5 parts of isobutyraldoxime and 10.5 partsof sodium in 300 parts by volume of absolute ethanol is added drop bydrop during 30 minutes at 5 C. to a mixture of 93 parts of 4-fiuoro-1,3-dinitrobenzene and 200 parts by volume of acetonitrile, whilestirring. The batch is then stirred for 3 hours at room temperature,diluted with ice water, filtered and recrystallized from acetonitrile.The product melts at 9 EXAMPLE 7 33 parts of a-methylaminopropionitrilein 200 parts by volume of dioxan are added drop by drop within 1 hour at50 C. while stirring to 69 parts of couminaldehydeoxirne-O-(-chloro-2,4-dinitro-phenyl ether) in 700 parts by volume ofdioxan, during which the temperature of the solution rises slightly.

After 1 hour, the batch is diluted with ice Water, filtered andrecrystallized from ethanol+dimethylformamide. The product melts at 161to 162 C.

EXAMPLE 10 10 f 2 N02 =N-O N02 CH: NH-(EHG-CH:

23 parts of isopropylamine in 100 parts of dioxan are added drop by dropduring 1 hour, at 50 C., to 77 parts of fluorenoneoxime-O-(S-chloro-2,4-dinitropheny1 ether) in 1500 parts by volume ofdioxan. The batch is then refluxed for 3 hours at 80 C., another 20parts of isopropylamine are added and the mixture is heated for 3 hoursat 80 C., diluted with ice water, filtered and digested with hotdimethylformamide. The product melts at 240 to 241 C. withdecomposition.

EXAMPLE 11 An oxime salt solution prepared from 86 parts of3,4-dichlorobenzaldoxime, 10.3 parts of sodium and 600 parts by volumeof absolute ethanol is added drop by drop at room temperature within /2hour to parts of isopropyl-(S- chloro-2,4-dinitrophenyl)sulphide in 400parts by volume of acetonitrile, while stirring. After 3 hours, thebatch is diluted with ice water, filtered and recrystallized fromacetonitrile. The product melts at 191 to 192 C.

EXAMPLE 12 (12) (IKJHs NO:

A thiophenolate solution prepared from sodium methylate and 29 parts of4-chlorothiophenol in 800 parts by volume of dioxan is added drop bydrop, under a current of nitrogen, during 30 minutes, to 63 parts ofZ-methoxybenzaldehydoxime-O-(S-chloro 2,4 dinitrophenyl ether) in 1000parts by volume of dioxan, while stirring. The batch is then heated for1 hour at 40 C., diluted with ice water, filtered and recrystallizedfrom dioxan-l-dimethylformamide. The product melts at 197l98 C.

The following oxime ethers of 2,4-dinitrophenols have been prepared byanalogous methods described in the foregoing examples:

C=NO N 02 TABLE 1 Compound Melting No. R: point, C.

Cl- OH= (CHa)zN- -C omNn-o-o--o11= HO- -CH= I 01 OH TABLE 1C0nt1n11edTABLE 2Continued C: C: Compound Melting Compound Melting No. R: point,C. 5 No. R; point, C. 55 CH1 1 183-184 68 CH3 126-127 Q-CHBr-CHBr-:

C 2 C(CH3)2 C: 56 214-215 7o 169-170 57-.-..:.:.:.;.--..' NO: 185-186CzHsO- CH:

0N OH= -CH=CHCH= 72 202-203 C1 -CH= 6o CH 155-156 73 CH1 68-69 0-GHQ-CH-= H 61 CH -OH= 95-96.5

CH CH 110-112 615 01 194-195 74 C-CH: HO -CH= C C:

l C=Cfi Ha Yellow 011. 1 Decomposition. o

4-1 The followmg ox1me ethers of 2,4-d1n1tro-5-ch1oro- 75 E 1 05 phenolwere prepared by methods analogous to those described in the foregoingexamples: 0 H; 0:

C=NO NO: 76 OH; (2 R2 1 l CHa-(CHMC:

TABLE 2 77 165-166 OH: C d /C= M In 78 N02 181-183 0111 01111 8 I1 0. pR: DO1I11Z, 0

01- -CH= 62 Cg; 130-131 79 3H1 (3H1 (2) CHa-COH--C= 63 CE; 92-94 80 02H:(2)

/C= CH3-(CH2)3C= CH5 CH=CH-C= 168-169 82 (3H3 C2Ha (2) CzH5'CH-CH2C=129-131 TABLE 2Continued TABLE 3-Contim1ed Compound Melting Com ound aMeltln No. R; point, C. 5 No. D Rz point, C s5 (13H: 148-149 95 31115 Ias cg; 143-144 oil-@ C 86 CH: CH:

1 l 9619. 01 175-176 CHr-CH-CHz-C: 1 1 om 186-187 15 HO-Q-CH:CHBrGHBr-C= 83 214-215 96b Br I 181-182 Br g 960 I 185-186 I 01 K Brown011. I Decomposition.

88b Br 1 187-189 The following oxime ethers of 2,4-din1tro-6-carbome- H03: thoxyphenol were prepared in a similar manner:

1 Br N 02 88c I 1 176-178 B1\ Ila/@011: /C=NO N02 R2 1 1 c o 0 CH3 1Decomposition. I Brown 01!. TABLE 4 The following oxime ethers of2-nitro-4-carbomethoxyno were re ared b methods analo ous to those de-0: 1 p P y g Compound Melting scnbed 1n the foregomg examples. R point,0.

C1- CH:

C=N-0COOCH: R 98 O M TABLE 3 R 99 Cl 105-107 Melting 0121:(3011111011116 2/ point} C.

61 123-124 100 13 137 90 OCH: CH:

101 OOH; 133-135 C10H= on:

65 CH3C= 01 CH: 103 (3H e m 93 1 185-186 CH: H0 CH= 104 CH3 0113om-wm-cm-o:

105 CH1 141-143 94 CH1 68-69 1 1 --CH=CH-C= (kHz-' nitropllenol weremanufactured anaogously:

The cyclohexanone oxime-2-nitro-4-N-methylsulphanylphenylether.(compound 1-34) melts at 129-130 Gr" Furthermore, the following oximeethers of 2,4-dinitro- S-aminophenol were manufactured analogously: I I

TABLE 9 R:

R1 10 c= R1 Compound Melting; No. R2 point, 0 0; Com '11 Meltln mun Rpoint, C 135 H 1 210 126 164-165 136 1491-150 (CaHQM CH= C H H 128 n 01147448 138 CH:CH-(CH2)1TC= V 113-11-4- A H H 1 139 gem-cm 187-188 1110:i 129--..:--: as: 157-158 4 C a 140 OCH; "158 3o 7 1 The following oximeethers of 1-nitro-4-N,N-dimethylo sulphamylphenol were manufacturedanalog usly Decomposition.

v C=N-O S 02N(CH1): The following oxime ethers of2,4-dinitro-5-isopropyl-V TABLE 8 ammophenol were manofactmedeoelogously:

0: Compound Meltln .N O No. 111 point, 0% R; a

130 Br 183-184 C=NO N03 H0 CH= Nil- 1 1(1) 1L1 TABLE 10 HO OH= CompoundMelting No. R: point, C. l 141 OCH; 146-147 132...": CH: 142-144 5 CHoH,-o 5

CH: CHr-C-CH: C= 142 ?Hz 159-160 v I CH O c=c11 l l33..--':;:-:.;CH;(]HC= 111-113 CH, C:

HI \CG: 133a- K 184-485 5 cm I w I The following oxime ethers werealsofimnufactured'in Dmmpwimm an analogous way to that described above.

Melting Compound No. Formula point, C.

Compound No. Formula m" n 1 .-r

157.--..:;::::...1 GHr-CHI 011 C I N:

CHr-C HCHaCH :N-O N Eamon.

CH| CH. CHr-(iH-JP-flQ-O NO.

CH 01H o,H|t':-o1r, $=N- o No,

' HCHlC I n.

CH; oar--o=N-o no,

Roman. 43H: 1u2.---..-.--. 1 No, 130-131 I- no- CH=NOQNO:

H-CHaCE on.

Decomposltiou.

EXAMPLE 13 (a) A mixture of 50 g. of the active ingredient No. 14, g. ofHisil (a silica preparation), g. of kaolin, 3.5 g. of flotation agent(for example a condensation product of 1 mol of para-octylphenol with 6to 10 mols of ethylene oxide) and 1.5 g. of a wetting agent (for examplethe sodium salt of 1-benzyl-2-heptadecylbenzirnidazole-disulphonic acid)is finely ground to form a wettable powder containing of the activeproduct.

The active ingredient No. 21 is formulated in a similar manner, exceptthat 25 g. of chalk are used instead of 25 g. of kaolin. In an identicalmanner, the active substance No. 14 of Example 4 is formulated.

and 67 are mixed 'with 110 g. of ammonium ligninsulphonate, 45 g." ofdicresyl methanedisulphonic acid, 10, g. 3

of a mixture of 40% of an alkylaryl-polyether alcohol and60% ofmagnesium carbonate, an d3-35 g. of kaolin. In each case,'-the resultingmixture may be diluted with water to form a stable emulsion.

EXAMPLE 14 (a) When usedfor a postemergence treatment, the fol-. lowingactive compoundsjproduced a good effect against (b) 500 grams each ofthe active ingredients Nos. 5 genuine leaves.

The following results were recorded:

Poa,

Dactylis and Lactuca, whereas others were not Compound number 1 Speciesof plant: Beta mtlg Phaseolus 8; wHHmW-S E a motootemsssooszo &.swcwSSEwSSSw wwmcwcawwros eo Compound number HHHD-H-H-IH H g vnhwoocccooco Species of plant:

Beta vulgarity.

top cal-58556285 w-cooamuoooEqooE Hooormco H =HH mSEEE wwoowsooasgsscancel-ma mas;

Sorghum- Phaseolus mowocnacoeosmmm M-QH ESQIEEEOQ slooo soogmwssocio'neosen ss cmci-u moe sssg soiooossoomsss solooo soommms GOHOMOSsm-lQ im-u o sg s s m-HQSQQESQSSQ Explanation: 0=no efiect. =damagethat spreads.

Each of the active compounds Nos. 5, 10, 20, 56, 67, 88 and 99,formulated as described in Example 13(b) was sprayed on the soil in anamount of 0.5 kg. per hectare, in a greenhouse test immediately aftersowingi.e. by the preemergence method. The test plants and the resultsachieved are listed in the following table:

N OTE.0=N0 efiect. =plant completely destroyed.

When applied in an amount of 0.5 kg. of active compound only a fewplants were strongly affected, above all Avena, -Poa, Dactylis andLactuca, whereas the others were not damaged at all or only to a verysmall etxent, such as Triticum, Hordeum, Brassica, Soya and Phaseolus.

(b) The active substances Nos. 5 and 67, formulated as described inExample 13 (b), in an amount of 4.0, 2.0, 1.0 and 0.5 kg. of activesubstance per hectare, were sprayed over the soil in a greenhouse testimmediately after seeding, that is to say, by the preemergence method.The seedlings treated and the results achieved are shown in thefollowing table:

Active substance Active substance No. 5 N o. 67

10 10 9 2 10 7 7 2 10 5 5 2 10 4 5 2 10 10 10 10 10 10 10 8 10 1O 10 1010 10 10 10 10 10 10 10 10 10 10 10 10 10 10 3 l0 9 8 3 10 10 5 3 10 4=2 1 10 10 10 10 10... 10 10 10 10 10 10 4 10 10 10 8 1O 7 4 1 9 4 2 1 51 1 1 4 1 0 0 Norn.0=no effect.

10=plant completely destroyed.

5=damage that results in the plant dying 05.

10=plant completely destroyed.

damaged at all or only 'very little, for example Triticum, Hordeum,Brassica, Soya and Phaseolus.

Accordingly, the two new active substances may be used as totalherbicides by the pre-cmergence method or, when used in a suitableconcentration, for the selective control of weeds, for example in graincrops (Triticum and Hordeum), varieties of cabbage (Brassica) andleguminoses (soybeans and Phaseolus beans).

EXAMPLE 15 Mixtures containing 50 g. of the active substances Nos. 16,20, 22, 4 and 66 each, 3.5 g. of a non-ionic, and 1.5 g. of an anionicwetting and dispersing agent are finely ground with 50 g. of a vehicle.The wettable spray powders thus obtained may be diluted with water inany desired proportion.

EXAMPLE 16 10 to 40 grams of each of the compounds 68, 73, 75, 98 76 and94 are made up with an adequate amount of an emulsifier(sulphonate-nonionic mixture) in xylene to a volume of 100 ml. Theseemulsion concentrates may be diluted with water to the desiredconcentration and used as fungicides.

EXAMPLE 17 The products of this invention, for example compound No. 16,are also distinguished by their action against genuine powdery mildew.Zucchetti plants (Cwcumis pepo) were trained in a greenhouse and oncesprayed prophylactically with a broth containing as active ingredient0.2% of the preparation formulated as described in Example 15. 2 daysafter having been sprayed, the plants were infested with spores ofErysiphe cichoracearum and 12 to 14 days later checked for fungusattack. Compared with the untreated control (efiect :nil) the sprayedplants displayed a efiect without having developed phytotoxic damage.

Effects similar to those against Erysiphe circoracearum described abovewere observed with the following compounds, which were readily toleratedby the Zucchetti plants:

27 EXAMPLE 1s The action of the compounds of this invention against leafspot. fungi was confirmed on celery (A pium graveolens) with the fungusSeptoria apii. Celery plants were trained in a greenhouse and, 2 daysbefore infection with the fungus Septoria, sprayed with broths eachcontaining 0.2% of one of the active compounds mentioned below. .Afterinfection, the plants were placed for 2 to 3 weeks in an incubation roomhaving a high atmospheric humidity and then checked for infestationagainst an untreated control series, which latter revealed a nil-return.The effects produced by the compounds of this invention are listed inthe following table:

Compound No.: Effect in percent 20 93 EXAMPLE 19 Herbicidal effect inthe greenhouse Preemergent Postemergent compound No. 99 compound No. 93

Kg. AS 2. o 1. o. s o. 25 s. 0 2. 5

Trlticum 10 9 7 0 0 Hordeum-- 10 9 7 4 0 0 Avalon--- 10 10 10 10 1 1Sorghum 8 4 2 1 2 1 Panicum 10 10 8 1 10 8 P08 10 10 10 8 6 2 Daetylis-10 1o 10 1o 4 2 Digitaria- 10 10 4 1 7 4 eta. 10 10 10 10 10 10Calendula- 1O 10 10 10 10 10 Linurn. 10 10 10 5 10 10 Brassica 10 10 7 810 10 Daucusu 10 10 10 10 10 10 Lactuca- 10 10 10 10 10 10 Soya 10 8 2 04 3 Phsseolus 10 10 1 O 8 5 When compound No. 99 was applied in anamount of 2 kg. or over, it displayed total herbicidal properties.

When a small amount, for example 0.25 kg., of the active substance ofthis invention is applied, numerous test plants can be completely oralmost completely destroyed without affecting, for example, soybean orphase-' olus bean plants. With even smaller amounts wild oats (Avenafatua) in barley (Hordeum) may be controlled. Compound No. 93, appliedin an amount of 2.5 kg., was successfully applied against numerousdicotyledons and Panicum, whereas the various types of grain crops werenot damaged by the active substance of the invention.

EXAMPLE 20 Test on grain crops in the field In a. field of winter wheatwhich had just been tilled and in which the weeds had reached the 4 leafstage, the compounds Nos. 18 and 26 were sprayed in an amount of 8.0 kg.per hectare. 3 weeks after the treatment, the effects achieved on weedswere found to be very good (that is to say value 1 and 2 respectively).Grain'crops, on the other hand, had not been damaged (value 1-2).

Test on salad in the open The compound No. 27 was sprayed in an amountof 8.0 kg. per hectare on salad four weeks after seeding (3-4 leafstage) and when the weeds had reached the stage of the large rosette.

The effect achieved on the weeds was good (value 3), whereas the saladwas not affected by the vherbicide of this invention.

Tests with marrow cabbage in the open Compound Compound No. 5 N o. 67

Amount used, kg. AS/ha 2. 0 3. 0 4. 0 3. 0 4. 0

Effect on weeds 3 3 2 2 2 Tolerance by culture plants--." 2 2 2 3 5EXAMPLE 21 All compounds to be tested were formulated in the usualmanner.

To check their acaricidal effect, Phaseolus plants in the 2-leaf stagewere infested 12 hours before the treatment by covering them with piecesof leaves infested by a mite species (Tetranychus telarius orTetranychus urticae; carmine red mite). 12 hours later, the test plantwas found to be covered with mites in all stages of development. Theactive ingredient, in the form of an emulsion, was sprayed with the aidof a fine sprayer over the plants in a manner such that a uniform layerof droplets was formed on the leaf surface. The mortality was checked 2and 7 days later and expressed in percent. The effect upon ova cannot bestated after the test had been run for 2 days as described because theaverage time taken by the larvae to leave the ova has not yet beenestablished.

At a concentration of 0.08% of active ingredient the following mortaliyvalues were found:

Ova, Larvae, Adults, percent percent percent Compound number:

1 After 2 days 100 100 After 7 days 100 100 100 2 After 2 days 100 100After 7 days 100 100 100 3 After 2 days 100 100 After 7 days 100 100 1004 After 2 days 100 100 After 7 days 100 100 100 5 After 2 days--- 100100 After 7 days 100 100 100 13- After 2 days 100 100 After 7 days. 100100 14 After 2 days 100 100 After 7 days- 100 100 100 15 After 2 da s100 100 After 7 days 100 29 After 2 days 100 100 After 7 days--. 100 100100 31 After 2 days- 100 100 After 7 days 80 100 100 45 After 2 days 100100 After 7 days 80 100 100 1 After 2 days 100 100 After 7 days 100 100100 46 After 2 days 100 100 After 7 dayS 100 100 100 58 After 2 days 100100.

After 7 days 80 100 100 72 After 2 days. 100 100 After 7 days.-- 80 100100 78 After 2 days 100 100 After 7 days 100 100 100 TABJL E Continued(1)) Action against Tetr. telarius Ova Larvae Adults percent percentpercent Mmtauty after Compound number: A d 100 100 2 days 7 days 91 ggi:100 100 100 5 00110., nil-m: Larvae Adults Ova Larvae Adults 101 After-2da s 100 100 0 100 100 After 7 digs. 100 000 100 :8 g 38 23 115 After 2days- 100 100 After 7 days 100 100 100 10 123 After 2 days .4 100 100After 7 days 100 100 100 COMPOUND No. 155

(a) Action against Tetr. urticae Mortality after- Compound No. 4,applied in a concentration of 0.05%, 2 d 7 d displayed a good killingeflfect against red spiders, for exre ample against Panonychus ulmi,Eotetranychus tiliae a 0" 1 pm Larvae Adults Ova Larvae Adults goodkilling efiect, in fact against both their ova a t 800 m0 100 60 100 80postembryonal stages. i831 g 80 ion The following compounds show atconcentrations of 0 00 0.05% the following mortality rate (o vicidaleflect) against Panonychus uimi (control after 7 days).

(b) Action against Tetr. telariua Moqahty rate Mortality after- CompoundNo.: in percent 3 95 2 days 7 days 9 l 100 Gone, p.p.m.' Larvae AdultsOva Larvae Adults 10 100 soc 100 so 0 100 100 21 100 400.. 100 so 0 soso 5 100 200 8 80 0 0 80 62 80 78 100 2 100 COMPOUND NO. 156 88 100 (a)Action against Tetr. urticae 95 100 M tali it 119 100 or ty a er 129 1002 days 7 days Conc., p.p.m. Larvae Adults Ova Larvae Adult In thefollowing tables also Tetranychus urticae which 100 100 100 100 100 isresistant to phosphorus acid esters is listed. 1% 3g igg 18g 100 100 6080 100 COMPOUND N0. 153

(a) Action against Tetr. urticae 1, Action against Tet, m m

after- Mortality after- 2 days 7 y 2 days 7 days Conc., p.p.m: LarvaeAdults Ova Larvae Adults gone, Larvae Adults o Larvae Adults 800 100 100100 100 100 100 100 100 100 100 mo 100 80 80 100 400 100 100 100 100 100100 100 0 80 80 I COMPOUND N0. 157 (b) Action agamst (a) Action againstTetr. urticae Mortality after- Mortality 2 days 7 days 2 days 7 daysCone" Larvae Adults Ova Larvae Adults Oonc., p.p.m. Larvae Adults OvaLarvae Adults 100 100 100 100 10c igg 3g 28 3g 100 100 80 80 100 so 8060 80 80 so 60 0 60 so COMPOUND NO. 154

(a) Action against Tetr. urticae (b) Action against Tetr. telarzusMortality aiter- Mortality after 2 days 7 days 7 2 days 7 days LarvaeAdults Ova Larvae Adults Conc., p.p.m. Larvae Adults Ova Larvae Adults ICOMPOUND Norma,

(13) Action against Tetr.'urtince Mortality'aiter I a: 2 days 7 days ICone, p.p.m. Larvae Adults Ova Larvae Adults (h) Action against Tetr.telarim Mortality aiter- 2 days 7 days Cone, p.p.m; Larvae Adults OvaLarvae Adults COMPOUND NO. 160

(a) Action against Tetr. urticae Mortality alter- 2 days 7 days Cone.,p.p.m. Larvae Adults Ova Larvae Adults (b) Action against Tetr. telariuaMortality after- W 2 days 7 days Coma, p.p.m. Larvae Adults Ova LarvaeAdults EXAMPLE 22 Compound No. 4, applied in a concentration of 0.05displayed a good killing efiect against red spiders, for example againstPanonychus ulmi, Eotetranychus tiliae, in fact against both their ovaand the post-embryonal stages.

Equally good results were observed with compounds Nos. 21 and 3.

' EXAMPLE 23 Freshly laid ova of the flour moth Ephestia kuehnz'ellaeach) were placed in folded paperfilters, the emulsi- Concentration ofactive substance in p.-p.m.: Percent killed 1000 i 100 500 100 250 100I25 100 62.5 1.00

What is claimed is: I

1. A compound of the formula o1 'NO: 1

wherein R is hydrogen or chlorine, and R is hydrogen or carbomethoxy. c

2. The compound of claim 1 of the formula 3. The compound of claim 1 ofthe formula a NO: i

References Cited UNITED STATESPATENTS 3,718,978 2/1913 Farrano etal260-471R LORRAINE A. WEINBERGER, Primary Examiner L. A. 'IHAXION,Assistant Examiner US. Cl. X.R. 260566 HE

